US3588625A - Electrolytic condenser and paste composition therefor - Google Patents
Electrolytic condenser and paste composition therefor Download PDFInfo
- Publication number
- US3588625A US3588625A US796181A US3588625DA US3588625A US 3588625 A US3588625 A US 3588625A US 796181 A US796181 A US 796181A US 3588625D A US3588625D A US 3588625DA US 3588625 A US3588625 A US 3588625A
- Authority
- US
- United States
- Prior art keywords
- paste composition
- electrolyte
- ethylene glycol
- electrolytic condenser
- boric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title abstract description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 55
- 239000003792 electrolyte Substances 0.000 abstract description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 17
- 239000004327 boric acid Substances 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 12
- 229920000728 polyester Polymers 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 description 12
- 230000003068 static effect Effects 0.000 description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 7
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- -1 aliphatic carboxylates Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-M arsenate(1-) Chemical compound O[As](O)([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- AUTNMGCKBXKHNV-UHFFFAOYSA-P diazanium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [NH4+].[NH4+].O1B([O-])OB2OB([O-])OB1O2 AUTNMGCKBXKHNV-UHFFFAOYSA-P 0.000 description 3
- FRRMMWJCHSFNSG-UHFFFAOYSA-N diazanium;propanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC([O-])=O FRRMMWJCHSFNSG-UHFFFAOYSA-N 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- PLYYQWWELYJSEB-DEOSSOPVSA-N (2s)-2-(2,3-dihydro-1h-inden-2-yl)-2-(9h-fluoren-9-ylmethoxycarbonylamino)acetic acid Chemical compound C1C2=CC=CC=C2CC1[C@@H](C(=O)O)NC(=O)OCC1C2=CC=CC=C2C2=CC=CC=C21 PLYYQWWELYJSEB-DEOSSOPVSA-N 0.000 description 2
- HJILUIYNJPLJSO-UAIGNFCESA-N (z)-but-2-enedioate;trimethylazanium Chemical compound C[NH+](C)C.C[NH+](C)C.[O-]C(=O)\C=C/C([O-])=O HJILUIYNJPLJSO-UAIGNFCESA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- HCUARRIEZVDMPT-UHFFFAOYSA-N Indole-2-carboxylic acid Chemical compound C1=CC=C2NC(C(=O)O)=CC2=C1 HCUARRIEZVDMPT-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- VINPSZVDTAURQW-UHFFFAOYSA-K aluminum;benzenesulfonate Chemical compound [Al+3].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 VINPSZVDTAURQW-UHFFFAOYSA-K 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- ONKCPRSKSOXPNX-UHFFFAOYSA-N barium(2+) hexaborate Chemical compound B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2] ONKCPRSKSOXPNX-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- OMAQJPSQYYDOKO-UHFFFAOYSA-M lithium;hydron;propanedioate Chemical compound [H+].[Li+].[O-]C(=O)CC([O-])=O OMAQJPSQYYDOKO-UHFFFAOYSA-M 0.000 description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 2
- 239000002370 magnesium bicarbonate Substances 0.000 description 2
- SMQOOYNBNZULBW-UHFFFAOYSA-L magnesium;ethanesulfonate Chemical compound [Mg+2].CCS([O-])(=O)=O.CCS([O-])(=O)=O SMQOOYNBNZULBW-UHFFFAOYSA-L 0.000 description 2
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 150000004707 phenolate Chemical class 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 229940103091 potassium benzoate Drugs 0.000 description 2
- 239000004300 potassium benzoate Substances 0.000 description 2
- 235000010235 potassium benzoate Nutrition 0.000 description 2
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- IZUPJOYPPLEPGM-UHFFFAOYSA-M sodium;hydron;phthalate Chemical compound [Na+].OC(=O)C1=CC=CC=C1C([O-])=O IZUPJOYPPLEPGM-UHFFFAOYSA-M 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 2
- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical compound [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 description 1
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000008881 Oenanthe javanica Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- CBIFDJDRCNEMQB-UHFFFAOYSA-N [Al].O[As](O)(O)=O Chemical compound [Al].O[As](O)(O)=O CBIFDJDRCNEMQB-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WLRJJCBQEQTZMV-UHFFFAOYSA-N n,n-dibutylbutan-1-amine;sulfuric acid Chemical compound [O-]S([O-])(=O)=O.CCCC[NH+](CCCC)CCCC.CCCC[NH+](CCCC)CCCC WLRJJCBQEQTZMV-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- JAUCIKCNYHCSIR-UHFFFAOYSA-M sodium;2-cyanoacetate Chemical compound [Na+].[O-]C(=O)CC#N JAUCIKCNYHCSIR-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- YNPXMOHUBANPJB-UHFFFAOYSA-N zinc;butan-1-olate Chemical compound [Zn+2].CCCC[O-].CCCC[O-] YNPXMOHUBANPJB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; Separators
Definitions
- the present invention relates to a paste composition used as an electrolyte for an electrolytic condenser.
- the typical known paste composition for an electrolytic condenser is a mixture of electrolyte compounds of borates and ethylene glycol.
- the borate of the mixture is added in amounts in excess of the upper limit of its solubility in ethylene glycol in order to furnish the condenser with good withstand voltage properties and great readiness for formation.
- such a composition has the drawbacks that it presents an unduly great viscosity at normal temperature due to the presence of a super-saturated borate, presents difficulties in being impregnated in a porous intermediate layer interposed ,between the electrodes of the condenser and fails properly to act as an electrolyte because of its tendency to solidify at low temperatures.
- Other disadvantages of the lrnown composition are, for example, that when used as an electrolyte in an electrolytic condenser, the composition 7 degrates the electrical properties and capacity stability of said composition when it is left unloaded.
- an electrolytic condenser formed of the composition is extremely stable to temperature variations and displays no noticeable change in its capacity even whenit is left unloaded for long hours.
- Electrolyte compounds available for preferable use in the pastecomposition of the present invention for an electrolytic condenser include one or more of boric acid, boric anhydride and borates such as ammonium tetraborate, ammonium pentaborate and barium hexaborate; phosphates such as potassium dihydrogen phosphate and zinc pyrophosphate; carbonates such as ammonium carbonate and magnesium bicarbonate; arsenates such as lithium dihydrogen arsenate and aluminurn arsenate; sulfates such as tributyl ammonium' sulfate and sodium hydrogen sulfate; acetates such as cadmium acetate and barium acetate; malonates such as lithium hydrogen malonate and diammonium malonate; aliphatic carboxylates such as magnesium acrylate, trimethylammonium maleate, ammonium tartrate and sodium cyan
- the boric acid polyesters of ethylene glycol used in the paste composition of the present invention may be prepared by subjecting boric acid or boric anhydride and ethylene glycol to dehydration and condensation reaction at a temperature of, for example, 90 to. I C and preferably in the presence of a catalyst.
- the nlol ecular weight of the polymer obtained is distributed between about 700 and about 750,000 in accordance with the propdrtions of the starting materials and reaction conditions involved.
- boric acid it is preferably mixed with ethylene glycol in the molar ratio of about 1:] or about 2:1.
- the molar ratio of boric anhydride to ethylene glycol is about 1:1.
- Ratios widely departing from the aforementioned limits are likely to generate a polymer insoluble in N-methyl-Z-pyrrolidon, and such polymer is unavailable for use in the present inyention.
- the water which is produced with the progress of condensation reaction of boric acid or boric anhydride with ethylene glycol should be removed by heating the reaction product. The reason is that the presence of waterreduces the stability of the paste composition at temperatures of less than 0 C. If an organic solvent such as toluene is added to the reaction mixture, followed by heating, then the elimination 10f water will be more easily effected due to the azeotropy of :water with toluene.
- the paste composition of the present invention consists of the boric acid polyesters of ethylene glycol and the abovelisted electrolyte compounds dissolved in N-methyl-Z-pyrrolidone.
- the N-methyl-2 -pyrrolidone itself has a favorable nature as the solvent component of an electrolyte and is capable of dissolving the electrolyte compounds and polyester polymers.
- This pyrrolidone the only material available at present for the purpose of the present invention. While there is no particular limitation on the proportions of the components of the paste compositioii of the present invention, experiments confirm that the following proportions are preferable.
- the paste composition of the present invention is chemically stable and not easily affected by temperature variations. For instance, when left unloaded 1,000 hours at a temperature of 80 C. the composition did not display any change in its pH, viscosity and specific resistivity, resulting in no occurrence of precipitates. Further, experiments show that when left unloaded for long a conderiser using this composition as an electrolyte exhibits far less variations in the capacity and leakage current than the one prepared from the prior art composition. Such favorable properties of the paste composition of the present invention will naturally help to obtain an electrolytic condenser displaying better performance than has been possible with the conventiohal paste composition.
- EXAMPLE 1 There were prepared in accordance with the recipe given in the table below 20 different polyester polymers of ethylene glycol.
- Azeotropy with butanol Azeotropy with butauol Reaction conditions Average molecular weight of Boric Ethylene Tempera- Pressure, Water rereaction Polynwr No add, g. glycol, g. ture, C. mm. Hg moved, g. product 33. 1 66. 9 140 760 28. 8 2, 200 33. 1 66. 9 100 50 28. 8 2, 000 33. l 66. 9 93 760 28. 8 1, 800 33. 4 66. 6 180 760 29. 7, 500 33. 4 66. 6 140 760 26. 0 8, 400 33. 4 66. 6 100 50 29. 0 13, 000 33. 4 66. 6 93 760 29. 0 8, 000 50. 0 50.
- the polymersthus prepared were all soluble in N-methyl-2- pyrrolidone.
- electrolyte compounds and N-methyl-Z-pyrrolidone were added to prepare eight different samples of a paste composition of the present invention. Determination was made of the pH, static viscosity, stability at high and low temperatures and breakdown voltage of each sample. Determination of a breakdown voltage was made by immersing in 50 cc. of the sample three aluminum foils 99.99 percent pure, 100 microns thick and cm. in surface area which has been washedwith water, degreased and cleaned with alcohol, followed by drying and arranged at a 30 space of mm. in parallel relationship, and carrying out constant current formation at a current density of 50 ma./dm. with the central foil used as an anode and those on both sides thereof as a cathode.
- the cylindrical body After being dried 1 hour at a temperature of 60 C. and a pressure .of 1 mm. Hg, the cylindrical body was immersed 4- hours in a sample paste composition at 60 C. at a pressure of 20 mm. Hg. The anode and cathode were fitted with a terminal and the cylindrical body was wound with kraft paper for insulation. Then the cylindrical body was. housed in an aluminum envelope which was closed at one end and had an insulation layer of pitch formed at said closed end. The open end of the envelope was encapped with a plate of insulating material in such a manner that the aforementioned anode and cathode terminals projected outside.
- EXAMPLE 2 denser was prepared in the order of the following steps. There was formed a cylindrical body consisting of an anode made of an aluminum foil 99.99 percent pure, 50 mm. wide, 950 mm. long, 94 microns thick and having a static capacity of 8.2 micro F/dm. which, after etching treatment, had been sub- 75' There were prepared in accordance with the recipe given in the table below 12 different boric acid polyester polymers of ethylene glycol. These polymers were all soluble in N-methyl- 2-pyrrolidone.
- Example 1 To some selected ones of the polymers prepared were added electrolyte compounds and N-methyl-Z-pyrrolidbne to form seven different sample paste compositions. There were further fabricated seven difierent electrolytic condensers using each of said samples in the same manner as in Example 1'. Determination was made of the properties of the resultant cyanoacetate, potassium benzoate, sodium hydrogen phthalate, strontium salicylate, magnesium ethane sulfonate, aluminum benzene-sulfonate, sodium alpha-naphthalenesulfonate, sodium phenolate, dilithium resorcinate, zinc picramate, ethylamine, ethylene diamine digutylamine,
- a paste composition for an electrolytic condenser consisting essentially of 0.5 to 30 weight percent electrolyte compound, 10 to 95 weight percent N-methyl-Z-pyrrolidone and 2 to 89.5 weight percent of boric acid polyesters of ethylene glycol having a molecular weight between about 700 and 750,000 and soluble in N- methyl-Z-pyrrolidone, said electrolyte compound being selected from the group consisting of boric acid, boric anhydride, salts of boric, phosphoric, pyrophosphoric, carbonic, arsenic, sulfuric, acetic, malonic, acrylic, maleic, tartaric, cyanoacetic, benzoic, phthalic, salicylic, alkyl sulfonic, and arylsulfonic acids, phenolates, aliphatic amines, aromatic amines and alkoxides.
- a paste composition of claim 1 wherein said electrolyte compound is selected from the group consisting of boric acid, boric anhydride, ammonium tetraborate, ammonium pentaborate, barium hexaborate, potassium dihydrogen phosphate, zinc pyrophosphate, ammonium carbonate, magnesium bicarbonate, lithium dihydrogen arsenate, aluminum arsenate, tributyl ammonium sulfate, sodium hydrogen sulfate, cadmium acetate, barium acetate, lithium hydrogen malonate, diammonium malonate, magnesium acryla te,
- a paste composition according to claim 1 wherein the boric acid polyesters of ethylene glycol are the condensation product of ethylene glycol and boric anhydride;
- An electrolytic condenser comprising a pair of aluminum foil electrodes, a porous layer interposed between said electrodes, a paste composition impregnated in said porous layer, an envelope housing said electrodes, porous layer and paste composition and terminals fitted to each of said electrodes to project outside said envelope, said paste composition consisting essentially of 0.5 to 30 weight percent electrolyte compound, 10 to 95 weight percent N-methyl-Z-pyrrolidone and 2 to 89.5 weight percent of boric acid polyesters of ethylene
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Abstract
A PLASTIC COMPOSITION CONSISTING OF ELECTROLYTE COMPOUNDS, BORIC ACID POLYESTERS OF ETHYLENE GLYCOL AND N-METHYL-2-PYRROLIDONE. WHEN USED AS AN ELECTROLYTE FOR AN ELECTROLYTIC CONDENSER, THE COMPOSITION FURNISHES SAID CONDENSER WITH GOOD ELECTRICAL PROPERTIES.
Description
\ United States Patent [72] Inventors Yasukane Kihara 1 Tokyo;
Ushimatsu Moriyama, F ujisawa-shi; Yoichi Sets, Yokohama-shi, J span [54] ELECTROLYTIC CONDENSER AND PASTE COMPOSITION THEREFOR v 5 Claims, No' Drawings [51'] Int.Cl.... HOIg9/02 [50] FieldofSearch 252/62.2; 317/230. (Chemical AbstructsO [56] References Cited UNITED STATES PATENTS 3,302,071 1/1967 Stahr 252/62.2X 3,351,823 11/1967 Jenny..... 252/62.2X 3,487,270 12/1969 Alwitt 252/62.2X
FOREIGN PATENTS 1,480,996 5/1967 France Primary Examiner-James E. Poer Assistant Examiner-J. Cooper Artorney Kemon, Palmer and Estabrook ABSTRACT: A paste composition consisting of electrolyte compounds, boric acid polyesters of ethylene glycol and N- methyI-Z-pyrrolidone. When used as an electrolyte for an electrolytic condenser, the composition furnishes said condenser with good electrical properties.
ELECTROLYTIC CONDENSER AND PASTE COMPOSITION THEREFOR BACKGROUND OF THE INVENTION The present invention relates to a paste composition used as an electrolyte for an electrolytic condenser.
The typical known paste composition for an electrolytic condenser is a mixture of electrolyte compounds of borates and ethylene glycol. The borate of the mixture is added in amounts in excess of the upper limit of its solubility in ethylene glycol in order to furnish the condenser with good withstand voltage properties and great readiness for formation. However, such a composition has the drawbacks that it presents an unduly great viscosity at normal temperature due to the presence of a super-saturated borate, presents difficulties in being impregnated in a porous intermediate layer interposed ,between the electrodes of the condenser and fails properly to act as an electrolyte because of its tendency to solidify at low temperatures. Other disadvantages of the lrnown composition are, for example, that when used as an electrolyte in an electrolytic condenser, the composition 7 degrates the electrical properties and capacity stability of said composition when it is left unloaded.
SUMMARY OF THE INVENTION preciably low temperatures of 35 C. or lower, but is capable of forming a-good electrode. Further, an electrolytic condenser formed of the composition is extremely stable to temperature variations and displays no noticeable change in its capacity even whenit is left unloaded for long hours.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Electrolyte compounds available for preferable use in the pastecomposition of the present invention for an electrolytic condenser include one or more of boric acid, boric anhydride and borates such as ammonium tetraborate, ammonium pentaborate and barium hexaborate; phosphates such as potassium dihydrogen phosphate and zinc pyrophosphate; carbonates such as ammonium carbonate and magnesium bicarbonate; arsenates such as lithium dihydrogen arsenate and aluminurn arsenate; sulfates such as tributyl ammonium' sulfate and sodium hydrogen sulfate; acetates such as cadmium acetate and barium acetate; malonates such as lithium hydrogen malonate and diammonium malonate; aliphatic carboxylates such as magnesium acrylate, trimethylammonium maleate, ammonium tartrate and sodium cyanoacetate; aromatic carboxylates such as potassium benzoate, sodium hydrogen phthalate, and strontium salicylate; sulfonates such as magnesium ethane sulfonate, aluminum benzenesulfonate and sodium a-naphthalenesulfonate; phenolates such as sodium phenolate, dilithium resorcinate and zinc picramate; aliphatic amines such as ethylamine, ethylene diamine, digutylamine and triethanolamine; aromatic amines such as aniline, pyridine, indolate and melamine; and alkoxides such as sodiumethoxide, potassium isopropoxide, and zinc ter-bu toxide.
The boric acid polyesters of ethylene glycol used in the paste composition of the present invention may be prepared by subjecting boric acid or boric anhydride and ethylene glycol to dehydration and condensation reaction at a temperature of, for example, 90 to. I C and preferably in the presence of a catalyst. The nlol ecular weight of the polymer obtained is distributed between about 700 and about 750,000 in accordance with the propdrtions of the starting materials and reaction conditions involved. Where boric acid is used, it is preferably mixed with ethylene glycol in the molar ratio of about 1:] or about 2:1. The molar ratio of boric anhydride to ethylene glycol is about 1:1. Ratios widely departing from the aforementioned limits are likely to generate a polymer insoluble in N-methyl-Z-pyrrolidon, and such polymer is unavailable for use in the present inyention. The water which is produced with the progress of condensation reaction of boric acid or boric anhydride with ethylene glycol should be removed by heating the reaction product. The reason is that the presence of waterreduces the stability of the paste composition at temperatures of less than 0 C. If an organic solvent such as toluene is added to the reaction mixture, followed by heating, then the elimination 10f water will be more easily effected due to the azeotropy of :water with toluene.
The paste composition of the present invention consists of the boric acid polyesters of ethylene glycol and the abovelisted electrolyte compounds dissolved in N-methyl-Z-pyrrolidone. The N-methyl-2 -pyrrolidone itself has a favorable nature as the solvent component of an electrolyte and is capable of dissolving the electrolyte compounds and polyester polymers. This pyrrolidone the only material available at present for the purpose of the present invention. While there is no particular limitation on the proportions of the components of the paste compositioii of the present invention, experiments confirm that the following proportions are preferable.
Electrolyte compounds 01.5 to 30 parts by weight Boric acid polyesters of ethylene glycol 2 to 89.5 parts by weight 1 N-methyl-2-pyrrolidone 1 0 to 9.5 parts by weight The paste composition of the present invention is chemically stable and not easily affected by temperature variations. For instance, when left unloaded 1,000 hours at a temperature of 80 C. the composition did not display any change in its pH, viscosity and specific resistivity, resulting in no occurrence of precipitates. Further, experiments show that when left unloaded for long a conderiser using this composition as an electrolyte exhibits far less variations in the capacity and leakage current than the one prepared from the prior art composition. Such favorable properties of the paste composition of the present invention will naturally help to obtain an electrolytic condenser displaying better performance than has been possible with the conventiohal paste composition.
Further characteristics and concrete advantage of the present invention will be more fully appreciated from the i 1 specific examples which follow.
EXAMPLE 1 There were prepared in accordance with the recipe given in the table below 20 different polyester polymers of ethylene glycol.
Azeotropy with butanol Azeotropy with butauol Reaction conditions Average molecular weight of Boric Ethylene Tempera- Pressure, Water rereaction Polynwr No add, g. glycol, g. ture, C. mm. Hg moved, g. product 33. 1 66. 9 140 760 28. 8 2, 200 33. 1 66. 9 100 50 28. 8 2, 000 33. l 66. 9 93 760 28. 8 1, 800 33. 4 66. 6 180 760 29. 7, 500 33. 4 66. 6 140 760 26. 0 8, 400 33. 4 66. 6 100 50 29. 0 13, 000 33. 4 66. 6 93 760 29. 0 8, 000 50. 0 50. 0 180 760 29. 0 44, 000 50. 0 50. 0 140 760 29. 0 75, 000 50. 0 50. 0 100 50 29. 0 35, 000 50. 0 50. 0 93 7 29. 0 60, 000 54. 0 46. O 180 7 26. 6 1, 056 54. 0 46. 0 140 760 26. 6 1, 000 54. (J 46. 0 100 50 26. 6 1, 200 54. 0 46. 0 93 760 26. 6 1, 100
The polymersthus prepared were all soluble in N-methyl-2- pyrrolidone.
To some selected ones of these polymers were added electrolyte compounds and N-methyl-Z-pyrrolidone to prepare eight different samples of a paste composition of the present invention. Determination was made of the pH, static viscosity, stability at high and low temperatures and breakdown voltage of each sample. Determination of a breakdown voltage was made by immersing in 50 cc. of the sample three aluminum foils 99.99 percent pure, 100 microns thick and cm. in surface area which has been washedwith water, degreased and cleaned with alcohol, followed by drying and arranged at a 30 space of mm. in parallel relationship, and carrying out constant current formation at a current density of 50 ma./dm. with the central foil used as an anode and those on both sides thereof as a cathode.
There were further prepared eight different condensers from the aforesaid eight different samples. Determinationwas made with each condenser of the reduction of the static capacity, dielectric loss and variations in the static capacity and the equivalent series resistance after the condenser was left unloaded 1,000 hours at a temperature of 85 C. The conjected to constant current formation in an aqueous solution'of ammonium borate until 600 volts were reached, a cathode made of an aluminum foil 99.99 percent pure, mm. wide, 1,000 mm. long and 50 microns thick, and an intermediate layer interposed between both poles which comprised a sheet of high density kraft paper mm. wide, 1,100 mm. long and 45 microns thick and a sheet of medium density kraft paper 65 mm. wide, 1,100 mm. long and 20 microns thick. After being dried 1 hour at a temperature of 60 C. and a pressure .of 1 mm. Hg, the cylindrical body was immersed 4- hours in a sample paste composition at 60 C. at a pressure of 20 mm. Hg. The anode and cathode were fitted with a terminal and the cylindrical body was wound with kraft paper for insulation. Then the cylindrical body was. housed in an aluminum envelope which was closed at one end and had an insulation layer of pitch formed at said closed end. The open end of the envelope was encapped with a plate of insulating material in such a manner that the aforementioned anode and cathode terminals projected outside.
The recipe and properties of the respective paste compositions and the properties of the condensers prepared therefrom are presented in the table below.
. tion, percent Sample Polymer, Wt. percent 60 50 15 39. 5 4 15 0 (14) (17) 35 20 40 70 60 75 17 5 10 15 0.5 6 10 3 5.8 5.5 6.1 6.3 5.0 1 168 158 76 303 36 84 2 No change in pH, specific resistivity and viscosity and no occurrence of precipitates.) Low temperature stability, 35 C. hrs (No solidification and no occurrence of precipitates.) Brcakdown voltage, V. 595 610 680 630 650 Reduction of static capac y due t 15 18 22 13 24 9 15 19 Dielectric loss, 12 s., 25 C 0. 05 0.03 0.04 0.05 0.02 0.04 Variations in static capacity, perce 1.0 2.0 1.0 1.0 5.0 1.0 ancc,S2,-30 2.8 0.4 1.2 0.9
l Cadmium acetate. I 3 Barium hcxaborate. 3 Tctramcthylammonium dihydrogen phosphate. 4 Zinc pit-rate. 5 Potassium benzoatc. i Ammonium tartratc. T Trirnethylammonium maleatc. Ethylamine.
EXAMPLE 2 denser was prepared in the order of the following steps. There was formeda cylindrical body consisting of an anode made of an aluminum foil 99.99 percent pure, 50 mm. wide, 950 mm. long, 94 microns thick and having a static capacity of 8.2 micro F/dm. which, after etching treatment, had been sub- 75' There were prepared in accordance with the recipe given in the table below 12 different boric acid polyester polymers of ethylene glycol. These polymers were all soluble in N-methyl- 2-pyrrolidone.
- Breakdown voltage, V
Azeotropy with hutanol Average Home Reaction conditions molecular anhy- Ethylene Water weight of dnde, glycol, Tcmpera- Pressure, removed, reaction Polymer .\-o. 1:. tune. C. nun. llg 1. product 20. 3 70. T 180 T 15.7 750 20.3 if 1-10 760 15.7 710 N. 3 79. T 100 50 15. 7 800 20. 3 7t). 7 J3 760 15. 7 740 21. l 78. 1 180 760 16. S 220, 000 21. fl 78. 1 140 760 16. 9 750. 000 21. 7S. 1 10) 50 16. 9 355.000 21. f1 78. 1 83 760 16. 9, 601, 000 21. 78. 5 180 7 16. 5 2, 900 21. 5 78. 5 140 J 7 16. 5 2, 500 21. 5 7S. 5 100 50 16. 5 3,100 21. 5 78. 5 93 760 16. 5 2,700
To some selected ones of the polymers prepared were added electrolyte compounds and N-methyl-Z-pyrrolidbne to form seven different sample paste compositions. There were further fabricated seven difierent electrolytic condensers using each of said samples in the same manner as in Example 1'. Determination was made of the properties of the resultant cyanoacetate, potassium benzoate, sodium hydrogen phthalate, strontium salicylate, magnesium ethane sulfonate, aluminum benzene-sulfonate, sodium alpha-naphthalenesulfonate, sodium phenolate, dilithium resorcinate, zinc picramate, ethylamine, ethylene diamine digutylamine,
triethanolamine, aniline, pyridine, indolate, melamine, sodium condensers. The table below gives the recipe and properties of each paste composition and the properties of each electrolytic ethoxide, potassium isopropoxide and zinc butoxide.
3. A paste composit on according to claim 1 wherein the 25 condenser. boric acid polyesters of ethylene glycol are the condensation Sample 0 1o 11 12 ,13 A 14 15 Polymer, wt. percent, 67 55 A 2 35 85 No (21 (22) (2 (26) (27) N-methyl-2-pyrrolidone, Wt. percent. 30. 5 05 45 66 82 10 Electrolyte compounds, wt. percent. 1 2. 5 2 3 3 4 10 8 7 5 pH, 250 c 5. 3 6. 4 6.1 6.5 4. 9 Static viscosity, cps., J C 114 181 7 472 286 540 High tempeiature stability, 16 0.. 111%.
Low temperature stability, -35 C 120 hrs Reduction of static @5561 211135 12115151 65121 38 (No change in pH, specific resistivity and viscosity and no occurrence of precipitates.) (No solidification and no occurrence of precipitates.) 650 590 720 680 tion, percent... 16 7 Dielectric loss, 12 c./s., 25 C 0.03 0.05 Variations in static capacity, percent 85 C..
1,000 hrs 3.0 Equivalent seri resistance, S2, -35 1.8
1 Calcium isoprox'ide.
2 Pyridine.
. Diammonium malonate.
4 Lithium dihydrogen arsenate. 5 Aluminum benzene-sulionate. 5 Magnesium acrylate. 7 Ammonium carbonate.
We claim:
1. A paste composition for an electrolytic condenser consisting essentially of 0.5 to 30 weight percent electrolyte compound, 10 to 95 weight percent N-methyl-Z-pyrrolidone and 2 to 89.5 weight percent of boric acid polyesters of ethylene glycol having a molecular weight between about 700 and 750,000 and soluble in N- methyl-Z-pyrrolidone, said electrolyte compound being selected from the group consisting of boric acid, boric anhydride, salts of boric, phosphoric, pyrophosphoric, carbonic, arsenic, sulfuric, acetic, malonic, acrylic, maleic, tartaric, cyanoacetic, benzoic, phthalic, salicylic, alkyl sulfonic, and arylsulfonic acids, phenolates, aliphatic amines, aromatic amines and alkoxides.
2. A paste composition of claim 1 wherein said electrolyte compound is selected from the group consisting of boric acid, boric anhydride, ammonium tetraborate, ammonium pentaborate, barium hexaborate, potassium dihydrogen phosphate, zinc pyrophosphate, ammonium carbonate, magnesium bicarbonate, lithium dihydrogen arsenate, aluminum arsenate, tributyl ammonium sulfate, sodium hydrogen sulfate, cadmium acetate, barium acetate, lithium hydrogen malonate, diammonium malonate, magnesium acryla te,
trimethyl ammonium maleate, ammonium tartr'ate, sodium product of ethylene glycol and boric acid.
4. A paste composition according to claim 1 wherein the boric acid polyesters of ethylene glycol are the condensation product of ethylene glycol and boric anhydride;
5. An electrolytic condenser comprising a pair of aluminum foil electrodes, a porous layer interposed between said electrodes, a paste composition impregnated in said porous layer, an envelope housing said electrodes, porous layer and paste composition and terminals fitted to each of said electrodes to project outside said envelope, said paste composition consisting essentially of 0.5 to 30 weight percent electrolyte compound, 10 to 95 weight percent N-methyl-Z-pyrrolidone and 2 to 89.5 weight percent of boric acid polyesters of ethylene
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP671668 | 1968-02-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3588625A true US3588625A (en) | 1971-06-28 |
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ID=11645974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US796181A Expired - Lifetime US3588625A (en) | 1968-02-05 | 1969-02-03 | Electrolytic condenser and paste composition therefor |
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| US (1) | US3588625A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4982963A (en) * | 1972-12-18 | 1974-08-09 | ||
| US4373176A (en) * | 1981-09-30 | 1983-02-08 | Sprague Electric Company | Electrolytic capacitor for at least 200 V service |
| DE3340167A1 (en) * | 1982-12-27 | 1984-06-28 | Emhart Industries, Inc., Indianapolis, Ind. | Electrolyte for an electrolytic capacitor |
| US6338806B1 (en) * | 1998-08-31 | 2002-01-15 | Matsushita Electric Industrial Co., Ltd. | Electrolytic capacitor and driving electrolyte thereof |
-
1969
- 1969-02-03 US US796181A patent/US3588625A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4982963A (en) * | 1972-12-18 | 1974-08-09 | ||
| JPS5716486B2 (en) * | 1972-12-18 | 1982-04-05 | ||
| US4373176A (en) * | 1981-09-30 | 1983-02-08 | Sprague Electric Company | Electrolytic capacitor for at least 200 V service |
| DE3340167A1 (en) * | 1982-12-27 | 1984-06-28 | Emhart Industries, Inc., Indianapolis, Ind. | Electrolyte for an electrolytic capacitor |
| US6338806B1 (en) * | 1998-08-31 | 2002-01-15 | Matsushita Electric Industrial Co., Ltd. | Electrolytic capacitor and driving electrolyte thereof |
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